CN111040378B - Solvent-free resin composition and application thereof - Google Patents
Solvent-free resin composition and application thereof Download PDFInfo
- Publication number
- CN111040378B CN111040378B CN201811206416.3A CN201811206416A CN111040378B CN 111040378 B CN111040378 B CN 111040378B CN 201811206416 A CN201811206416 A CN 201811206416A CN 111040378 B CN111040378 B CN 111040378B
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- Prior art keywords
- epoxy resin
- resin composition
- filler
- hollow
- weight
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 133
- 239000003822 epoxy resin Substances 0.000 claims abstract description 184
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 184
- 239000000945 filler Substances 0.000 claims abstract description 90
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000004848 polyfunctional curative Substances 0.000 claims abstract description 23
- 239000011256 inorganic filler Substances 0.000 claims abstract description 14
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 14
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- 229920003986 novolac Polymers 0.000 claims description 23
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 19
- -1 organobentonite Chemical compound 0.000 claims description 18
- 239000003063 flame retardant Substances 0.000 claims description 15
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 7
- 239000005995 Aluminium silicate Substances 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 235000012211 aluminium silicate Nutrition 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000000454 talc Substances 0.000 claims description 6
- 229910052623 talc Inorganic materials 0.000 claims description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 5
- 239000003086 colorant Substances 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 239000013008 thixotropic agent Substances 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052582 BN Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 3
- 239000007822 coupling agent Substances 0.000 claims description 3
- 229910002026 crystalline silica Inorganic materials 0.000 claims description 3
- 239000005350 fused silica glass Substances 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 239000003607 modifier Substances 0.000 claims description 3
- 239000006082 mold release agent Substances 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 3
- 101100016026 Drosophila melanogaster GstE14 gene Proteins 0.000 claims description 2
- 239000004599 antimicrobial Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 150000004693 imidazolium salts Chemical class 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 25
- 239000007788 liquid Substances 0.000 description 23
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 21
- 239000000126 substance Substances 0.000 description 21
- 238000011049 filling Methods 0.000 description 20
- 238000010521 absorption reaction Methods 0.000 description 19
- 238000012360 testing method Methods 0.000 description 19
- 239000004593 Epoxy Substances 0.000 description 18
- 150000002460 imidazoles Chemical class 0.000 description 16
- 239000003989 dielectric material Substances 0.000 description 13
- 229930185605 Bisphenol Natural products 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 150000001412 amines Chemical class 0.000 description 10
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 10
- 239000011889 copper foil Substances 0.000 description 10
- 238000001723 curing Methods 0.000 description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000004020 conductor Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000013007 heat curing Methods 0.000 description 5
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000004843 novolac epoxy resin Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 3
- HDPBBNNDDQOWPJ-UHFFFAOYSA-N 4-[1,2,2-tris(4-hydroxyphenyl)ethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 HDPBBNNDDQOWPJ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- 150000001409 amidines Chemical class 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- PULOARGYCVHSDH-UHFFFAOYSA-N 2-amino-3,4,5-tris(oxiran-2-ylmethyl)phenol Chemical compound C1OC1CC1=C(CC2OC2)C(N)=C(O)C=C1CC1CO1 PULOARGYCVHSDH-UHFFFAOYSA-N 0.000 description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
- ANOPCGQVRXJHHD-UHFFFAOYSA-N 3-[3-(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]propan-1-amine Chemical compound C1OC(CCCN)OCC21COC(CCCN)OC2 ANOPCGQVRXJHHD-UHFFFAOYSA-N 0.000 description 2
- 229920003319 Araldite® Polymers 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000003934 aromatic aldehydes Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 description 1
- DPZSNGJNFHWQDC-ARJAWSKDSA-N (z)-2,3-diaminobut-2-enedinitrile Chemical compound N#CC(/N)=C(/N)C#N DPZSNGJNFHWQDC-ARJAWSKDSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- SXSUUFZWSVMTRL-UHFFFAOYSA-N 1,2-dibromo-3-(2,3-dibromophenoxy)benzene Chemical compound BrC1=CC=CC(OC=2C(=C(Br)C=CC=2)Br)=C1Br SXSUUFZWSVMTRL-UHFFFAOYSA-N 0.000 description 1
- YUAPUIKGYCAHGM-UHFFFAOYSA-N 1,2-dibromo-3-(2,3-dibromopropoxy)propane Chemical compound BrCC(Br)COCC(Br)CBr YUAPUIKGYCAHGM-UHFFFAOYSA-N 0.000 description 1
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- LCXFHGRFFYYUSF-UHFFFAOYSA-N 2-ethyl-5-methyl-1H-imidazole Chemical compound C(C)C=1NC=C(N1)C.C(C)C=1NC=C(N1)C LCXFHGRFFYYUSF-UHFFFAOYSA-N 0.000 description 1
- KXRDLLZZOQGICO-UHFFFAOYSA-N 2-heptadecyl-1H-imidazole Chemical compound C(CCCCCCCCCCCCCCCC)C=1NC=CN1.C(CCCCCCCCCCCCCCCC)C=1NC=CN1 KXRDLLZZOQGICO-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 description 1
- AHIPJALLQVEEQF-UHFFFAOYSA-N 4-(oxiran-2-ylmethoxy)-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1COC(C=C1)=CC=C1N(CC1OC1)CC1CO1 AHIPJALLQVEEQF-UHFFFAOYSA-N 0.000 description 1
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- VMONJZJCURPWAB-UHFFFAOYSA-N BrC1=C(C(=C(C=C1)CCC1=C(C(=C(C=C1)Br)Br)Br)Br)Br.BrC1=C(C(=C(C=C1)CCC1=C(C(=C(C=C1)Br)Br)Br)Br)Br Chemical compound BrC1=C(C(=C(C=C1)CCC1=C(C(=C(C=C1)Br)Br)Br)Br)Br.BrC1=C(C(=C(C=C1)CCC1=C(C(=C(C=C1)Br)Br)Br)Br)Br VMONJZJCURPWAB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- RQOYAKOLGFETTH-UHFFFAOYSA-N NC=1N=C(CCCC2OCC3(CO2)COC(OC3)CCCC3=NC(=NC(=N3)N)N)N=C(N1)N Chemical compound NC=1N=C(CCCC2OCC3(CO2)COC(OC3)CCCC3=NC(=NC(=N3)N)N)N=C(N1)N RQOYAKOLGFETTH-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- UUQQGGWZVKUCBD-UHFFFAOYSA-N [4-(hydroxymethyl)-2-phenyl-1h-imidazol-5-yl]methanol Chemical compound N1C(CO)=C(CO)N=C1C1=CC=CC=C1 UUQQGGWZVKUCBD-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- MRNZSTMRDWRNNR-UHFFFAOYSA-N bis(hexamethylene)triamine Chemical compound NCCCCCCNCCCCCCN MRNZSTMRDWRNNR-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- FRCAGVUKJQCWBD-UHFFFAOYSA-L iodine green Chemical compound [Cl-].[Cl-].C1=CC(N(C)C)=CC=C1C(\C=1C=CC(=CC=1)[N+](C)(C)C)=C/1C=C(C)C(=[N+](C)C)C=C\1 FRCAGVUKJQCWBD-UHFFFAOYSA-L 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 125000005474 octanoate group Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- CCDXIADKBDSBJU-UHFFFAOYSA-N phenylmethanetriol Chemical compound OC(O)(O)C1=CC=CC=C1 CCDXIADKBDSBJU-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical class OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0094—Filling or covering plated through-holes or blind plated vias, e.g. for masking or for mechanical reinforcement
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/42—Plated through-holes or plated via connections
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/18—Spheres
- C08L2205/20—Hollow spheres
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/11—Printed elements for providing electric connections to or between printed circuits
- H05K1/115—Via connections; Lands around holes or via connections
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0104—Properties and characteristics in general
- H05K2201/012—Flame-retardant; Preventing of inflammation
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0209—Inorganic, non-metallic particles
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- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/09—Shape and layout
- H05K2201/09209—Shape and layout details of conductors
- H05K2201/095—Conductive through-holes or vias
- H05K2201/0959—Plated through-holes or plated blind vias filled with insulating material
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0011—Working of insulating substrates or insulating layers
- H05K3/0044—Mechanical working of the substrate, e.g. drilling or punching
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Abstract
The present invention provides a solvent-free resin composition comprising: (A) an epoxy resin component comprising at least two multifunctional epoxy resins, each multifunctional epoxy resin having at least three epoxy groups in each molecule; (B) an epoxy resin hardener; and (C) an inorganic filler comprising a hollow filler and a non-hollow spherical filler, wherein the weight ratio of the hollow filler to the non-hollow spherical filler is 1: 5 to 6: 1.
Description
Technical Field
The present invention relates to a solvent-free resin composition, and more particularly, to a solvent-free thermosetting filling resin composition (thermal curing filling resin composition) including an epoxy resin, a hollow filler and a non-hollow spherical filler, and a printed circuit board using the same.
Background
The printed circuit board can be used as a substrate of an electronic device, can carry a plurality of electronic components which can be electrically communicated with each other, and provides a stable circuit working environment. Due to the development of High Density Interconnect (HDI), the width and spacing of conductive lines on a printed circuit board are continuously reduced and the density of conductive lines is continuously increased, and the conventional printed circuit board structure is not applied to the HDI circuit design, and various new forms of printed circuit board structures are produced.
Generally, a printed circuit board is formed by alternately laminating a resin dielectric layer and conductor circuit layers, wherein a plurality of holes are formed between the conductor circuit layers, and the holes are plated with a conductive material to form through holes (via), thereby electrically connecting the conductor circuit layers. In order to meet the requirements of preventing damage of the outer layer circuit, making the thickness of the resin dielectric layer uniform, and serving as a basis for the upper stacked via structure, the via holes must be completely filled and polished to be flat, and the resin composition for filling the via holes must have desirable mechanical, electrical, and physical and chemical properties.
TW 399398 discloses a filling composition comprising an epoxy resin which is liquid at room temperature, a phenol resin which is liquid at room temperature, a curing catalyst and an inorganic filler, which composition shrinks only a little during thermosetting and has low hygroscopicity after curing. TW 200402429 discloses a solventless filling material including a filler, an epoxy resin, a dicyandiamide curing agent and a curing catalyst, which can provide a better adhesion of a conductive layer thereon and prevent the conductive layer, an insulating layer, a solder resist layer, etc. laminated on the filling material from being detached or cracked. TW 201437276 discloses an epoxy resin composition for filling, which comprises an epoxy resin, an imidazole compound, a borate compound and an inorganic filler, and which has good storage stability and heat resistance and can reduce the chance of voids and cracks during grinding. CN 103030931 discloses a thermosetting resin filling material comprising an epoxy resin, an epoxy resin curing agent and an inorganic filler, wherein the epoxy resin curing agent is selected from the group consisting of modified aliphatic polyamines (modified aliphatic polyamines) and modified alicyclic polyamines, and the thermosetting resin filling material has storage stability for long-term storage at room temperature and good filling workability.
Recently, with the development of high frequency, high speed and miniaturization of electronic products, dielectric materials with low dielectric constant (Dk) and low dielectric loss factor (Df) are increasingly applied to printed circuit boards. Therefore, there is a high demand for a thermosetting resin composition for filling having a low Dk value to meet the market demand.
Disclosure of Invention
In view of the above-mentioned technical problems, the present invention provides a solvent-free resin composition for filling holes in printed circuit boards, wherein the resin composition has excellent filling properties (printability) by using a hollow filler and a non-hollow spherical filler in combination, the filled holes do not generate defects such as bubbles, cracks or voids, and the resulting dielectric material after curing of the resin composition has a low dielectric constant (Dk) value, a low dielectric dissipation factor (Df) and excellent high temperature moisture resistance and heat resistance.
Accordingly, it is an object of the present invention to provide a solvent-free resin composition comprising:
(A) an epoxy resin component comprising at least two multifunctional epoxy resins, each multifunctional epoxy resin having at least three epoxy groups in each molecule;
(B) an epoxy resin hardener; and
(C) the inorganic filler comprises a hollow filler and a non-hollow spherical filler, wherein the weight ratio of the hollow filler to the non-hollow spherical filler is 1: 5 to 6: 1.
in some embodiments of the invention, the epoxy resin component (a) comprises at least two multifunctional epoxy resins selected from the group consisting of: phenol novolac type epoxy resin, aminophenol type epoxy resin, alkylphenol novolac type epoxy resin, bisphenol novolac type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, glycidylamine type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetraphenolethane type epoxy resin, diglycidyl phthalate resin, epoxy obtained by condensation of phenols and aromatic aldehydes having phenolic hydroxyl groups, bromine-containing epoxy resin and phosphorus-containing epoxy resin thereof, triglycidyl isocyanurate, alicyclic epoxy resin, liquid alcohol ether type epoxy resin, and fluorene type epoxy resin.
In some embodiments of the present invention, the epoxy resin component (a) includes a phenol novolac type epoxy resin and an aminophenol type epoxy resin, wherein the weight ratio of the phenol novolac type epoxy resin to the aminophenol type epoxy resin may be 1: 3 to 3: 1.
in some embodiments of the present invention, the epoxy resin hardener (B) is selected from the group consisting of: imidazole, imidazole derivatives, imidazole salts, salts of imidazole derivatives, and combinations thereof.
In some embodiments of the present invention, the weight ratio of the hollow filler to the non-hollow spherical filler is 1: 3 to 4: 1.
in some embodiments of the invention, the hollow filler is a hollow glass filler or a hollow silica filler.
In some embodiments of the invention, the material of the non-hollow spherical filler is selected from the group consisting of: crystalline silica, fused silica, barium sulfate, calcium carbonate, silicon nitride, aluminum nitride, boron nitride, aluminum oxide, magnesium oxide, aluminum hydroxide, magnesium hydroxide, titanium oxide, mica, talc, organobentonite, kaolin, Nojenberg silica, sintered kaolin clay, sintered talc, sintered Nobo silica, and combinations thereof.
In some embodiments of the present invention, the content of the epoxy resin hardener (B) is 1 to 20 parts by weight based on 100 parts by weight of the epoxy resin component (a).
In some embodiments of the present invention, the inorganic filler (C) is contained in an amount of 40 to 200 parts by weight based on 100 parts by weight of the epoxy resin component (a).
In some embodiments of the present invention, the epoxy resin component (a) further comprises a monofunctional epoxy resin, a difunctional epoxy resin, or a combination thereof.
In some embodiments of the invention, the resin composition further comprises an additive selected from the group consisting of: flame retardants, colorants, viscosity modifiers, thixotropic agents, defoamers, leveling agents, coupling agents, mold release agents, surface modifiers, plasticizers, antimicrobials, mildewcides, stabilizers, antioxidants, phosphors, and combinations thereof. Wherein the flame retardant may for example be selected from the group: phosphorus-containing flame retardants, bromine-containing flame retardants, and combinations thereof.
Another object of the present invention is to provide a printed circuit board having a hole filled with the resin composition as described above.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, several embodiments accompanied with figures are described in detail below.
Drawings
Fig. 1a to 1c are schematic views showing one embodiment of forming a filled printed circuit board of the present invention.
Fig. 2a to 2c are schematic views showing another embodiment of forming a filled printed circuit board of the present invention.
Description of the reference numerals
1. 2: printed circuit board
11. 21: dielectric layer
12. 22, 26: conductor circuit layer
13. 23, 25: hole(s)
14. 24: a resin composition.
Detailed Description
Some specific embodiments according to the present invention will be specifically described below; the invention may, however, be embodied in many different forms without departing from the spirit thereof, and the scope of the invention should not be construed as limited to the embodiments set forth herein.
As used in this specification (and particularly in the claims), the terms "a," "an," "the," and similar referents are to be construed to cover both the singular and the plural, unless otherwise indicated herein.
Unless otherwise indicated herein, the ingredients contained in a solution, mixture, or composition are described in this specification in terms of solids (dry weight), i.e., the weight of the solvent not included.
Unless otherwise specified, the term "solvent-free" in the present specification means that the content of the solvent is 5% by weight or less, preferably 3% by weight or less, more preferably 1% by weight or less, based on the total weight of the resin composition.
Generally, the solvent in the resin composition is volatilized by heating during the heat curing of the resin composition. However, in the case where a through hole in a printed circuit board has a high aspect ratio (aspect ratio), if the through hole is filled with a resin composition containing a solvent, a part of the solvent remains in the filled through hole after heat curing, and it is difficult to discharge the solvent. Therefore, in the subsequent printed circuit board process, the residual solvent expands due to heating, and bubbles or cracks are formed in the through holes, so that the printed circuit board is subjected to poor conditions such as layering or cracking, and the qualification rate of the printed circuit board is reduced. The solvent-free resin composition can effectively reduce or avoid bubbles and cracks from being formed in the filled through holes, thereby reducing or avoiding the poor conditions of layering, cracking and the like of the printed circuit board and realizing higher qualification rate. The related technical features and effects of the present invention will now be described in some embodiments as follows.
1. Solvent-free resin composition
The solvent-free resin composition of the present invention comprises (A) an epoxy resin component, (B) an epoxy resin curing agent, and (C) an inorganic filler. The details of each component are as follows.
(A) epoxy resin component
The epoxy resin component (a) includes at least two polyfunctional epoxy resins having at least three epoxy groups in each molecule.
Examples of the polyfunctional epoxy resin include, but are not limited to, the following epoxy resins having at least three epoxy groups: phenol novolac type epoxy resins, aminophenol type epoxy resins (particularly triglycidyl aminophenol type epoxy resins), alkylphenol novolac type epoxy resins, bisphenol novolac type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, glycidylamine type epoxy resins, trishydroxyphenylmethane type epoxy resins, tetraphenolethane type epoxy resins, phthalic acid diglycidyl ester resins, epoxy compounds obtained by condensing phenols (including biphenol, bisphenol, cresol and the like) and aromatic aldehydes having phenolic hydroxyl groups, and epoxy resins containing bromine and phosphorus, triglycidyl isocyanurate, alicyclic epoxy resins, liquid alcohol ether type epoxy resins and fluorene type epoxy resins. The bisphenol novolac epoxy resin includes novolac epoxy resins having a bisphenol structure, such as bisphenol a novolac epoxy resins and bisphenol F novolac epoxy resins. In a preferred embodiment of the present invention, the epoxy resin component (a) includes a phenol novolac type epoxy resin having at least three epoxy groups and an aminophenol type epoxy resin.
Preferably, at least one of the polyfunctional epoxy resins in the epoxy resin component (a) is liquid at 10 to 30 ℃. Thus, in some embodiments of the present invention, the epoxy resin component (a) may have the following combination of multifunctional epoxy resins: a combination of two polyfunctional epoxy resins which are liquid at 10 to 30 ℃, a combination of a polyfunctional epoxy resin which is liquid at 10 to 30 ℃ and a polyfunctional epoxy resin which is solid at 10 to 30 ℃ or a combination of two polyfunctional epoxy resins which are solid at 10 to 30 ℃, and the epoxy resin component (a) preferably has a combination of a polyfunctional epoxy resin which is liquid at 10 to 30 ℃ and a polyfunctional epoxy resin which is solid at 10 to 30 ℃, more preferably has a combination of two polyfunctional epoxy resins which are liquid at 10 to 30 ℃.
Examples of the liquid polyfunctional epoxy resin include, but are not limited to, the following epoxy resins having at least three epoxy groups: liquid phenol novolac type epoxy resin, liquid aminophenol type epoxy resin (particularly triglycidyl aminophenol type epoxy resin), liquid alkylphenol novolac type epoxy resin, liquid bisphenol novolac type epoxy resin, liquid naphthalene type epoxy resin, liquid dicyclopentadiene type epoxy resin, liquid glycidylamine type epoxy resin, liquid trihydroxyphenyl methane type epoxy resin, liquid tetraphenolethane type epoxy resin, liquid diglycidyl phthalate resin, liquid alicyclic epoxy resin, and liquid alcohol ether type epoxy resin.
In some embodiments of the present invention, the epoxy resin component (a) includes a liquid phenol novolac type epoxy resin having at least three epoxy groups and a liquid aminophenol type epoxy resin.
Commercially available products of phenol novolac type epoxy resins include, but are not limited to, jER 152 and jER 154 available from Mitsubishi CHEMICAL corporation, DEN 431, DEN 485 and DEN 438 available from DOW CHEMICAL corporation, and Epiclon N740 available from DIC corporation. Examples of the aminophenol type Epoxy resin include, but are not limited to, N, N, O-triglycidyl-p-aminophenol (e.g., jER630 available from Mitsubishi chemical company, Sumi-Epoxy ELM-100 and ELM-120 available from Sunto chemical company, and Araldite MY0500 and MY0600 available from Huntsman chemical company), and N, N, N ', N' -tetraglycidyl diaminodiphenylmethane (e.g., jER 604 available from Mitsubishi chemical company, Sumi-Epoxy ELM-434 available from Sunto chemical company, Araldite MY9634 and MY-720 available from Huntsman chemical company, and Epothto YH434 available from Dongdu chemical company). In some embodiments of the present invention, the epoxy resin component (a) includes a phenol novolac type epoxy resin jER 152 and an aminophenol type epoxy resin jER 630.
In the epoxy resin component (a), the content of each polyfunctional epoxy resin can be adjusted as required in principle, but the content of each polyfunctional epoxy resin is not yet too low in order to ensure the synergistic effect of using a plurality of polyfunctional epoxy resins in combination. Taking the case where the epoxy resin component (a) includes two polyfunctional epoxy resins, a phenol novolac type epoxy resin and an aminophenol type epoxy resin, the weight ratio of the phenol novolac type epoxy resin and the aminophenol type epoxy resin is preferably 1: 3 to 3: 1, more preferably 7: 13 to 7: 3, e.g. 7: 12. 7: 11. 7: 10. 7: 9. 7: 8. 1: 1. 7: 6. 7: 5 or 7: 4.
the epoxy resin component (a) may further include a monofunctional or bifunctional epoxy resin as required in addition to the polyfunctional epoxy resin, and may further include, for example, a bisphenol type epoxy resin and/or a bisphenol type epoxy resin. Examples of bisphenol-type epoxy resins include, but are not limited to, bisphenol a-type epoxy resins, hydrogenated bisphenol a-type epoxy resins, brominated bisphenol a-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, and bixylenol-type epoxy resins. In some embodiments of the present invention, the epoxy resin component (A) includes bisphenol A type epoxy resins and bisphenol F type epoxy resins.
(B) epoxy resin hardener
The epoxy resin hardener (B) means a hardener for accelerating hardening of an epoxy resin, the kind thereof is not particularly limited, and any of the well-known conventional substances which can be used as hardeners of the epoxy resin component (a) can be used, and examples thereof include, but are not limited to: imidazole, an imidazole derivative, an imidazole salt, a salt of an imidazole derivative, an amine, an amidine, an organophosphine compound and an acid anhydride, and imidazole, an imidazole derivative, an imidazole salt and a salt of an imidazole derivative are preferable. Each of the epoxy resin hardeners may be used alone or in combination of two or more.
Examples of imidazoles or imidazole derivatives include, but are not limited to: 2-ethyl-4-methylimidazole (2-ethyl-4-methylimidazole) and azine (azine) derivatives thereof, 2-undecylimidazole (2-undecyclimidazole), 2-heptadecylimidazole (2-heptadecylimidazole), 2-phenylimidazole, azine derivatives of 2-methylimidazole, 2-phenyl-4, 5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole. Examples of salts of imidazole salts or imidazole derivatives include, but are not limited to: isocyanurates of 2-phenylimidazole and of azine derivatives of 2-methylimidazole. Commercially available products include imidazoles or imidazole derivatives such as 2E4MZ-A, C11Z, C17Z, 2PZ, 2MZ-A, and 2E4MZ-A, isocyanurates of imidazoles such as 2MA-OK, 2MZ-OK, and 2PZ-OK, and imidazole methylol esters such as 2PHZ and 2P4MHZ, which are available from four national chemical industries.
Examples of amines include, but are not limited to: dicyandiamide and derivatives thereof, melamine and derivatives thereof, diamino maleonitrile and derivatives thereof, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, bis (hexamethylene) triamine, triethanolamine, diaminodiphenylmethane, organic acid dihydrazide and 3, 9-bis (3-aminopropyl) -2,4,8, 10-tetraoxaspiro [5,5] undecane. For example, the ATU type product from Ajinomoto (Ajinomoto) is an amine-based epoxy hardener.
Examples of amidines include, but are not limited to, octanoates, sulfonates of 1, 8-diazabicyclo [5,4,0] undecene-7. For example, the product model DBU from SAN-APRO belongs to amidine type epoxy hardener.
Examples of organophosphinic compounds include, but are not limited to: triphenylphosphine, tricyclohexylphosphine, tributylphosphine, methyldiphenylphosphine, and the like.
Examples of anhydrides include, but are not limited to: tetrapropenylsuccinic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenylsuccinic anhydride, methylendomethylenetetrahydrophthalic anhydride, and the like.
Among the epoxy resin hardeners, imidazole is particularly excellent in heat resistance and chemical resistance, and also has hydrophobicity, and can provide an effect of suppressing moisture absorption. In addition, guanamine such as dicyandiamide, melamine, methylguanamine, benzoguanamine, 3, 9-bis [2- (3, 5-diamino-2, 4, 6-triazabenzyl) ethyl ] -2,4,8, 10-tetraoxaspiro [5,5] undecane, derivatives thereof, organic acid salts thereof, epoxy adducts thereof, and the like can improve the adhesion between the dielectric material obtained from the resin composition and the copper foil and can provide rust resistance, contributing to the prevention of copper discoloration of the printed wiring board. In some embodiments of the present invention, 2MZ-A and 2E4MZ-A are used as the epoxy resin hardener (B).
In the resin composition of the present invention, the content of the epoxy resin hardener (B) is preferably 1 to 20 parts by weight, more preferably 1 to 10 parts by weight, for example, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 parts by weight, or 9 parts by weight, based on 100 parts by weight of the epoxy resin component (a). Without being limited by theory, within the preferred ranges specified above, the epoxy resin hardener (B) is effective in promoting the hardening of the epoxy resin, particularly without affecting the properties of the other components of the resin composition.
(C) inorganic Filler
The resin composition of the present invention relates to the use of a combination of specific inorganic fillers, i.e., the inorganic filler (C) comprises a hollow filler and a non-hollow spherical filler, and thus the present invention can have technical effects of enhancing the thermal conductivity, thermal expansibility and mechanical strength of the dielectric material made of the resin composition.
In the present invention, the hollow filler means a filler having a cavity inside, and the kind thereof is not particularly limited. The most common hollow fillers are made of glass or silica, and in addition, hollow fillers made of quartz, phenolic resins, carbon or thermoplastic resins, or surface-modified hollow fillers may be used. In some embodiments of the invention, the hollow filler has a D50 average particle size of 1 to 500 microns, preferably 1 to 200 microns, more preferably 10 to 100 microns, a wall thickness of 0.1 to 20 microns, and a density of 0.1 to 0.5 g/cc. Examples of hollow fillers include, but are not limited to, the following commercially available products: glass bunbles K1, K15, K20, K25, K37, K46, S22, S38, S60, S60J, S60HS, VS5500, S42XHS, iM16K, and iM30K, available from 3M company; commercially available from Potters-Ballotini
110P8、60P 18、34P30、25P45、
5020. 5020FPS, 7014, 7040S, Ceramic Multi Cellular CMC-20, CMC-15L and Extendpospheres SG; and is available from JGC C&C. Company threadhrear 1110. The above hollow filler may be used alone or two or more kinds may be selected and used in combination.
The kind of the non-hollow spherical filler is not particularly limited, and may be any filler commonly used for resins, and may generally have an average particle diameter of 0.1 to 25 micrometers, preferably 0.1 to 10 micrometers. Examples of non-hollow sphere fillers include, but are not limited to, non-metallic fillers such as crystalline silica, fused silica, barium sulfate, calcium carbonate, silicon nitride, aluminum nitride, boron nitride, alumina, magnesium oxide, aluminum hydroxide, magnesium hydroxide, titanium oxide, mica, talc, organobentonite, kaolin, noniberg silica (Silitin), sintered kaolin clay, sintered talc, sintered Noburg silica, and the like. The above non-hollow spheres may be used alone or two or more kinds may be selected for use in combination.
In some embodiments of the invention, the inorganic filler (C) employs S60 and iM30k, available from 3M company, as hollow fillers and SC-2500-SEJ and SC-6500-SXD, available from ADMATECHS company, as non-hollow spherical fillers.
In the resin composition of the present invention, the content ratio of the hollow filler to the non-hollow spherical filler is preferably 1: 5 to 6: 1, more preferably 1: 4 to 5: 1, optimally 1: 3 to 4: 1, e.g. 2: 5. 1: 2. 2: 3. 1: 1. or 2: 1. it has been found that when the hollow filler and the non-hollow spherical filler are used in the above preferred ratio, the resin composition has a better filling (printing) property, and the resulting dielectric material has a better electrical property and heat resistance.
In some embodiments of the present invention, the inorganic filler (C) may be contained in an amount of 40 to 200 parts by weight, preferably 45 to 180 parts by weight, more preferably 50 to 160 parts by weight, for example, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight, 95 parts by weight, 100 parts by weight, 105 parts by weight, 110 parts by weight, 115 parts by weight, 120 parts by weight, 125 parts by weight, 130 parts by weight, 135 parts by weight, 140 parts by weight, 145 parts by weight, 150 parts by weight or 155 parts by weight, based on 100 parts by weight of the epoxy resin component (a).
(D) other additives as required
Other components, such as additives existing in the art, may be included in the resin composition of the present invention as needed to specifically improve physicochemical properties of a dielectric material obtained by hardening the resin composition or processability of the resin composition during the manufacturing process. Examples of existing additives include, but are not limited to: flame retardants, colorants, viscosity modifiers, thixotropic agents (thixotropic agents), antifoaming agents (polydimethylsiloxanes, modified silicones, fluorine-containing polymers, polymeric surfactants, emulsion type agents, etc.), leveling agents (leveling agents), coupling agents, mold release agents, surface modifiers, plasticizers, antibacterial agents, antifungal agents, stabilizers, antioxidants, and phosphors. These additives may be used singly or in combination of two or more selected. The dosage of each additive is obtained by adjusting according to the needs according to the general knowledge after the content of the present specification is known to those skilled in the art, and is not described herein.
In some embodiments of the invention, the resin composition further comprises a flame retardant. Examples of flame retardants include, but are not limited to: a phosphorus-containing flame retardant, a bromine-containing flame retardant, or a combination thereof. Phosphorus-containing flame retardants such as metal hypophosphites, phosphoric esters, phosphazenes, ammonium polyphosphates, melamine phosphates, and melamine cyanurates; bromine-containing flame retardants such as tetrabromobisphenol a (tetrabromobisphenol a), decabromodiphenyl oxide (decabromodiphenyloxide), decabrominated diphenylethane (decabrominated diphenylethane), 1, 2-bis (tribromophenyl) ethane (1, 2-bis (tribromophenyl) ethane), brominated epoxy oligomer (brominated epoxy oligomer), octabromotrimethylphenyl indene (octobromomethylphenyl index), bis (2,3-dibromopropyl ether) (bis (2, 3-dibromophenyl ether)), tris (tribromophenyl) triazahydrazine (tris (brominated) triazine), brominated aliphatic hydrocarbon (brominated aliphatic hydrocarbon) and brominated aromatic hydrocarbon (brominated aromatic hydrocarbon).
In some embodiments of the invention, the resin composition further comprises a colorant. The colorant may be an ink that generally has print grade resistance, examples of which include, but are not limited to: phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black.
2. Printed circuit board
The resin composition of the present invention can be used for filling holes (e.g., through holes) of printed circuit boards, and therefore, the present invention further provides a filled printed circuit board having holes filled with the resin composition of the present invention. The method of forming the filled printed circuit board is described below with reference to the accompanying drawings.
Fig. 1a to 1c are schematic views illustrating an embodiment of forming the printed circuit board. As shown in fig. 1a, the printed circuit board 1 has a dielectric layer 11, a conductive circuit layer 12 and a hole 13. As illustrated in fig. 1b, the resin composition 14 of the present invention may be filled in the holes 13 of the printed circuit board 1 by a conventional patterning method, examples of which include, but are not limited to, a screen printing method, a roll coating method, a die coating method, and a spray coating method, and then the filled resin composition 14 is heated to a predetermined temperature to be hardened, and the holes may include through or non-through holes, such as plated through holes (plated holes), buried holes (buried vias), blind holes (blind vias), or recesses between conductor circuits. Thereafter, the hardened portions protruding from the printed circuit board 1 are ground or polished away by a grinding device to make the surface thereof flat, as shown in fig. 1 c.
The heat curing of the above resin composition may be performed in two stages in order to facilitate the sanding or polishing. Specifically, the filled resin composition may be heated to semi-cure, for example at a temperature of 90 ℃ to 150 ℃ for 30 to 90 minutes, and after grinding or polishing, the semi-cured filled resin composition may be heated to fully cure, for example at a temperature of 140 ℃ to 250 ℃ for 30 to 90 minutes. The hardness of the semi-cured product can be controlled by changing the heating temperature and the heating time.
Fig. 2 a-2 c illustrate a preferred method of fabricating a pcb structure, and the contents thereof can be referred to as TW 525417, which is hereby incorporated by reference in its entirety. As shown in fig. 2a, the printed circuit board 2 has a dielectric layer 21, a conductive circuit layer 22 and a hole 23. As shown in FIG. 2b, the resin composition 24 of the present invention can be filled into the holes 23, and then the holes 25 with smaller diameter than the holes 23 are formed in the resin composition 24, and then the walls of the holes 25 are metalized to form the conductive circuit layer 26 with smaller diameter. This produces a structure having the resin composition 24 interposed between the conductor circuit layers 22 and 26, as shown in FIG. 2 c.
3. Examples of the embodiments
The invention will now be further illustrated by the following specific embodiments, in which the measuring instruments and methods used are as follows:
[ viscosity test ]
0.2 ml of the resin composition was taken as a test sample, and measured using a cone plate type viscometer (model: TV-30, manufactured by Toyobo industries Co., Ltd.) under test conditions such as a test temperature of 25 ℃, a test rotation speed of 5rpm, and a test time of 30 seconds, to obtain a viscosity value of the resin composition.
[ filling Property (printability) test ]
A glass fiber epoxy substrate on which plated through holes had been formed in advance by plate plating was prepared, the plate thickness of the substrate being 1.6 mm and the diameter of the plated through holes being 0.8 mm. The resin composition was filled into the plated through-holes by a screen printing method, and then the filled glass fiber epoxy-based board was placed in a hot air circulating drying oven and heat-cured at temperatures of 110 ℃ and 150 ℃ for 30 minutes and 60 minutes, respectively, thereby preparing an evaluation sample. The sample was subjected to physical polishing and grinding, and the polished and ground sample was placed under an optical microscope at a magnification of 100 times, and the cross sections of 100 filled plated through holes were observed. The evaluation criteria are as follows: all plated through holes were completely filled (less than 3 unfilled) and recorded as "∘"; only a few vias were not completely filled (4 to 9 unfilled numbers), recorded as "Δ"; and the resin composition flowed out of the bottom of the through-hole or did not fill the through-hole (not filled up to 10 or more), recorded as "gamma".
[ Water absorption test ]
Coating the resin composition on a bright copper foil by a doctor blade, placing the bright copper foil coated with the resin composition in a hot air circulating drying furnace, subjecting to heat curing treatment at 110 deg.C and 150 deg.C for 30 minutes and 60 minutes, removing the resin composition from the bright copper foil, and evaluating the sample to obtain a sample weight (W) 1 ) Then, the sample was subjected to a moisture absorption test under PCT conditions (121 ℃, 100% r.h., 24 hours), and the weight (W) of the sample after moisture absorption was measured 2 ) The water absorption of the resin composition was calculated according to the following equation.
Water absorption of [ (W) 2 -W 1 )/W 1 ]×100％
[ glass transition temperature (Tg) test ]
The resin composition was applied to a bright copper foil by a doctor blade, the bright copper foil coated with the resin composition was placed in a hot air circulation type drying furnace, heat-cured at 110 ℃ and 150 ℃ for 30 minutes and 60 minutes, and then the resin composition was removed from the bright copper foil, and the glass transition temperature of the sample was measured by thermomechanical analysis (TMA).
[ measurement of dielectric constant (Dk) and dielectric dissipation factor (Df) ]
The resin composition was coated on the bright copper foil by a doctor blade, the bright copper foil coated with the resin composition was placed in a hot air circulation type drying furnace, heat-cured at 110 ℃ and 150 ℃ for 30 minutes and 60 minutes, and then the resin composition was removed from the bright copper foil. The dielectric constant and dielectric loss of the resin composition were measured at an operating frequency of 1GHz according to the specifications of ASTM D150.
[ test for Heat resistance after moisture absorption ]
A glass fiber epoxy substrate in which through-holes were formed by plate plating (panel plating) was prepared, the thickness of the glass fiber epoxy substrate was 1.6 mm and the diameter of the through-holes was 0.8 mm. The evaluation sample was prepared by filling the resin composition into the through-holes of the glass fiber epoxy-based plate by the screen printing method, and then placing the filled glass fiber epoxy-based plate in a hot air circulation type drying furnace, followed by heat-curing treatment at temperatures of 110 ℃ and 150 ℃ for 30 minutes and 60 minutes. The sample is firstly placed under PCT conditions (121 ℃, 100% R.H., 24 hours) for moisture absorption test, the sample after moisture absorption is physically polished and ground, the polished and ground sample is soaked in solder liquid at 288 ℃ for 10 seconds for three times, and then the sample is kept still to be cooled to the room temperature. The cross-sections of the 100 filled plated through-holes were observed with an optical microscope, and the number of through-holes in which the hardened resin composition had cracks was recorded. The evaluation criteria are as follows: when the number of cracked through holes in the cured resin composition was less than 3, the heat resistance was excellent and recorded as "∘"; if the number of cracked through holes of the resin composition after curing was 4 to 9, it showed slightly poor heat resistance, and was recorded as "Δ"; when the number of cracked through holes of the cured resin composition reached 10 or more, the heat resistance was the worst and recorded as "gamma".
3.1. Preparation of resin composition
Resin compositions of examples 1 to 11 and comparative examples 1 to 5 were produced in the following manner according to the compositions and contents shown in table 1. Wherein the bisphenol A type epoxy resin jER828 (from Mitsubishi chemical company) and the bisphenol F type epoxy resin KF-8100 (from Kolon company) are bifunctional epoxy resins; phenol novolac type epoxy resin jER 152 (available from mitsubishi chemical company) and amine phenol epoxy resin jER630 (available from mitsubishi chemical company) are multifunctional epoxy resins having at least three epoxy groups in each molecule.
[ example 1]
Phenol novolac type epoxy resin jER 152 (available from mitsubishi chemical company), amine phenol epoxy resin jER630 (available from mitsubishi chemical company), epoxy resin hardener 2MZ-A (available from mitsunobu chemical company), hollow filler iM30k (available from 3M company), non-hollow spherical filler SC-6500-SXD (available from ADMATECHS company) and defoamer KS-66 (available from shin-Etsu chemical industry company) were premixed at room temperature in the proportions shown in table 1, and kneaded and dispersed using three rolls to prepare solvent-free resin composition 1.
[ example 2]
[ example 3]
Resin composition 3 was prepared in the same manner as resin composition 1, except that the amounts of phenol novolac type epoxy resin jER 152 and amine phenol epoxy resin jER630 were adjusted as shown in table 1.
[ example 4]
Resin composition 4 was prepared in the same manner as resin composition 1, except that the amounts of phenol novolak-type epoxy resin jER 152 and amine phenol epoxy resin jER630 were adjusted as shown in table 1.
[ example 5]
Resin composition 5 was prepared in the same manner as in the preparation of resin composition 1, except that the amounts of phenol novolak-type epoxy resin jER 152, amine phenol epoxy resin jER630, hollow filler iM30k, and non-hollow spherical filler SC-6500-SXD were adjusted, and further bisphenol a-type epoxy resin jER828 (available from mitsubishi chemical) was added as shown in table 1.
[ example 6]
Resin composition 6 was prepared in the same manner as resin composition 5, except that bisphenol F type epoxy resin KF-8100 (available from Kolon corporation) was substituted for bisphenol A type epoxy resin jER828, and epoxy resin hardener 2E4MZ-A (available from four nations chemical Co., Ltd.) was substituted for epoxy resin hardener 2MZ-A, as shown in Table 1.
[ example 7]
[ example 8]
Resin composition 8 was prepared in the same manner as resin composition 3, except that the amounts of hollow filler iM30k and non-hollow spherical filler SC-6500-SXD were adjusted as shown in Table 1.
[ example 9]
Resin composition 9 was prepared in the same manner as resin composition 1, except that the amounts of hollow filler iM30k and non-hollow spherical filler SC-6500-SXD were adjusted as shown in Table 1.
[ example 10]
Resin composition 10 was prepared in the same manner as resin composition 1, except that the amounts of hollow filler iM30k and non-hollow spherical filler SC-6500-SXD were adjusted as shown in Table 1.
[ example 11]
Comparative example 1
Comparative resin composition 1 was prepared in the same manner as resin composition 1 was prepared, except that phenol novolac type epoxy resin jER 152 and amine phenol epoxy resin jER630 were substituted with bisphenol a type epoxy resin jER828 and bisphenol F type epoxy resin KF-8100 having no at least three epoxy groups per molecule, as shown in table 1.
Comparative example 2
Comparative example 3
Comparative resin composition 3 was prepared in the same manner as resin composition 1, but with the replacement of non-hollow spherical filler SC-6500-SXD by comminuted filler 525ARI (available from Silicoccoco) as shown in Table 1.
Comparative example 4
Comparative resin composition 4 was prepared in the same manner as in the preparation of resin composition 1, except that hollow filler iM30k was not used, only non-hollow spherical filler SC-6500-SXD was used, and the amount of non-hollow spherical filler SC-6500-SXD was adjusted as shown in Table 1.
Comparative example 5
Comparative resin composition 5 was prepared in the same manner as resin composition 1 was prepared, except that non-hollow spherical filler SC-6500-SXD was not used, only hollow filler iM30k was used, and the amount of hollow filler iM30k was adjusted as shown in table 1.
Comparative example 6
Comparative resin composition 6 was prepared in the same manner as resin composition 3, except that the proportions of hollow filler iM30k and non-hollow spherical filler SC-6500-SXD were adjusted so that the weight ratio of hollow filler to non-hollow spherical filler was less than 1: 5, as shown in table 1.
Comparative example 7
Table 1: compositions of resin compositions of examples 1 to 11 and comparative examples 1 to 7
3.2. Testing of the resin composition
The resin compositions obtained in examples 1 to 11 and comparative examples 1 to 7 were subjected to a viscosity test, a filling property (printability) test, a water absorption test, a glass transition temperature (Tg) test, dielectric constant (Dk) and dielectric dissipation factor (Df) measurements, and a heat resistance test after moisture absorption, and the measurement results are shown in table 2.
Table 2: test results of resin composition
As shown in table 2, the solvent-free resin composition of the present invention has a suitable viscosity and excellent filling properties (printability), and the filled holes do not have defects such as bubbles, cracks, or voids. The dielectric material obtained after the resin composition is cured can have low Dk and low Df value, and excellent heat resistance (Tg) and heat resistance after moisture absorption. In contrast, the experimental results of the comparative examples show: when the resin composition contains only the bisphenol type epoxy resin (comparative example 1), the dielectric material obtained from the resin composition is poor in heat resistance after moisture absorption; when the resin composition contains only one polyfunctional epoxy resin having at least three epoxy functional groups (comparative example 2), the dielectric material obtained from the resin composition has a high water absorption rate and poor heat resistance after moisture absorption; when the resin composition uses only the hollow filler and the pulverized filler and does not use the non-hollow spherical filler (comparative example 3), the viscosity of the resin composition is high and the filling property (printability) is poor; when the resin composition uses only the non-hollow spherical filler and does not use the hollow filler (comparative example 4), the Dk value of the dielectric material obtained from the resin composition is high; when the resin composition uses only the hollow filler, but does not use the non-hollow spherical filler (comparative example 5), the viscosity of the resin composition is high, and the water absorption rate of the dielectric material prepared from the resin composition is high, and the heat resistance after moisture absorption is poor; when the weight ratio of the hollow filler and the non-hollow spherical filler of the resin composition is less than 1: when 5 is used (comparative example 6), the Dk value of the dielectric material obtained from the resin composition is relatively high; and when the weight ratio of the hollow filler to the non-hollow spherical filler of the resin composition is more than 6: in case 1 (comparative example 7), the dielectric material obtained from the resin composition had a relatively high water absorption rate and poor heat resistance after moisture absorption.
Claims (11)
1. A solvent-free resin composition, comprising:
(A) an epoxy resin component comprising at least two multifunctional epoxy resins, each multifunctional epoxy resin having at least three epoxy groups in each molecule;
(B) an epoxy resin hardener; and
(C) the inorganic filler comprises a hollow filler and a non-hollow spherical filler, wherein the weight ratio of the hollow filler to the non-hollow spherical filler is 1: 3 to 4: 1,
wherein the epoxy resin component (A) includes a phenol novolac type epoxy resin and an aminophenol type epoxy resin.
2. The resin composition according to claim 1, wherein the weight ratio of the phenol novolac type epoxy resin to the aminophenol type epoxy resin is 1: 3 to 3: 1.
3. the resin composition of claim 1, wherein the epoxy resin hardener (B) is selected from the group consisting of: imidazole, imidazolium salts, and combinations thereof.
4. The resin composition according to claim 1, wherein the hollow filler is a hollow glass filler or a hollow silica filler.
5. The resin composition of claim 1, wherein the non-hollow spherical filler is selected from the group consisting of: crystalline silica, fused silica, barium sulfate, calcium carbonate, silicon nitride, aluminum nitride, boron nitride, aluminum oxide, magnesium oxide, aluminum hydroxide, magnesium hydroxide, titanium oxide, mica, talc, organobentonite, kaolin, Nojenberg silica, sintered kaolin clay, sintered talc, sintered Nobo silica, and combinations thereof.
6. The resin composition according to any one of claims 1 to 5, wherein the content of the epoxy resin hardener (B) is 1 to 20 parts by weight based on 100 parts by weight of the epoxy resin component (A).
7. The resin composition according to any one of claims 1 to 5, wherein the content of the inorganic filler (C) is 40 to 200 parts by weight based on 100 parts by weight of the epoxy resin component (A).
8. The resin composition according to any one of claims 1 to 5, wherein the epoxy resin component (A) further comprises a monofunctional epoxy resin, a difunctional epoxy resin, or a combination thereof.
9. The resin composition according to any one of claims 1 to 5, further comprising an additive selected from the group consisting of: flame retardants, colorants, viscosity modifiers, thixotropic agents, defoamers, leveling agents, coupling agents, mold release agents, surface modifiers, plasticizers, antimicrobials, mildewcides, stabilizers, antioxidants, phosphors, and combinations thereof.
10. The resin composition of claim 9, wherein the flame retardant is selected from the group consisting of: phosphorus-containing flame retardants, bromine-containing flame retardants, and combinations thereof.
11. A printed circuit board having a hole filled with the resin composition according to any one of claims 1 to 10.
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| Application Number | Priority Date | Filing Date | Title |
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| TW107136066A TWI698484B (en) | 2018-10-12 | 2018-10-12 | Solvent-free resin composition and uses of the same |
| TW107136066 | 2018-10-12 |
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| EP3882927A4 (en) * | 2018-11-15 | 2022-07-06 | Kyocera Corporation | Organic insulator, metal-clad laminate, and wiring board |
| TWI765482B (en) * | 2020-03-20 | 2022-05-21 | 聯茂電子股份有限公司 | Resin composition, prepreg, and printed circuit board |
| US20230063808A1 (en) * | 2021-09-02 | 2023-03-02 | Apple Inc. | Coaxial via shielded interposer |
| TW202406969A (en) * | 2022-03-24 | 2024-02-16 | 日商味之素股份有限公司 | Curable composition |
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- 2018-10-12 TW TW107136066A patent/TWI698484B/en active
- 2018-10-17 CN CN201811206416.3A patent/CN111040378B/en active Active
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2019
- 2019-01-16 US US16/249,667 patent/US10836919B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08225632A (en) * | 1995-02-21 | 1996-09-03 | Matsushita Electric Works Ltd | Sealing epoxy resin composition and semiconductor device sealed therewith |
| CN1316447A (en) * | 2000-04-06 | 2001-10-10 | 日东电工株式会社 | Epoxy resin composition for semi-conductor packaging and semi-conductor device using the composition |
| JP2002294035A (en) * | 2001-04-03 | 2002-10-09 | Nippon Kayaku Co Ltd | Epoxy resin composition and powdered paint |
| CN101016402A (en) * | 2003-01-07 | 2007-08-15 | 积水化学工业株式会社 | Curing resin composition, adhesive epoxy resin paste, adhesive epoxy resin sheet, conductive connection paste, conductive connection sheet, and electronic component joined body |
| CN102165583A (en) * | 2008-10-10 | 2011-08-24 | 住友电木株式会社 | Semiconductor device |
| JP2015010146A (en) * | 2013-06-28 | 2015-01-19 | 太陽インキ製造株式会社 | Thermosetting resin composition, and printed wiring board |
Also Published As
| Publication number | Publication date |
|---|---|
| US20200115572A1 (en) | 2020-04-16 |
| TW202014466A (en) | 2020-04-16 |
| CN111040378A (en) | 2020-04-21 |
| US10836919B2 (en) | 2020-11-17 |
| TWI698484B (en) | 2020-07-11 |
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